US9828387B2 - Control of color-body formation in isohexide esterification - Google Patents

Control of color-body formation in isohexide esterification Download PDF

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US9828387B2
US9828387B2 US15/102,281 US201415102281A US9828387B2 US 9828387 B2 US9828387 B2 US 9828387B2 US 201415102281 A US201415102281 A US 201415102281A US 9828387 B2 US9828387 B2 US 9828387B2
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isohexide
acid
product mixture
color
ester
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US20170022214A1 (en
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Kenneth Stensrud
Erik Hagberg
Erin Rockafellow
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Archer Daniels Midland Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters

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  • the present disclosure relates to certain cyclic bi-functional materials that are useful as monomers in polymer synthesis, as well as plasticizers, surfactants and intermediate chemical compounds.
  • the present invention pertains to esters of 1,4:3,6-dianhydrohexitols and methods for their preparation.
  • carbohydrates One of the most abundant kinds of biologically-derived or renewable alternative feedstock for such materials is carbohydrates.
  • Carbohydrates are generally unsuited to current high temperature industrial processes.
  • carbohydrates such as sugars are complex, multi-functionalized hydrophilic materials.
  • researchers have sought to produce biologically-based chemicals that can be derived from carbohydrates, but which are less highly functionalized, including more stable bi-functional compounds, such as 2,5-furandicarboxylic acid (FDCA), levulinic acid, and 1,4:3,6-dianhydrohexitols.
  • FDCA 2,5-furandicarboxylic acid
  • levulinic acid 1,4:3,6-dianhydrohexitols.
  • 1,4:3,6-Dianhydrohexitols are derived from renewable resources from cereal-based polysaccharides.
  • Isohexides embody a class of bicyclic furanodiols that derive from the corresponding reduced sugar alcohols, for example depending on the chirality, D-sorbitol, D-mannitol, and D-iditol are dehydrated and cyclized to A) isosorbide, B) isomannide, and C) isoidide, respectively, the structures of which are illustrated in Scheme A.
  • the isohexides are composed of two cis-fused tetrahydrofuran rings, nearly planar and V-shaped with a 120° angle between rings.
  • the hydroxyl groups are situated at carbons 2 and 5 and positioned on either inside or outside the V-shaped molecule. They are designated, respectively, as endo or exo.
  • Isoidide has two exo hydroxyl groups, while the hydroxyl groups are both endo in isomannide, and one exo and one endo hydroxyl group in isosorbide.
  • the presence of the exo substituents increases the stability of the cycle to which it is attached.
  • exo and endo groups exhibit different reactivities since they are more or less accessible depending on the steric requirements of the derivatizing reaction.
  • the present disclosure relates, in part, to a method for preparing esters from isohexide ester.
  • the method involves reacting an isohexide and an organic acid, in the presence of a reducing Br ⁇ nsted acid catalyst at a temperature up to about 250° C., for a time sufficient to produce the isohexide ester while limiting formation of color bodies in a product mixture to an APHA value of less than 230.
  • the method further includes reducing incumbent color bodies or color-generating precursor compounds in a preparation of the isohexide or organic acid prior to esterification with the reducing Br ⁇ nsted acid catalyst.
  • FIG. 1 depicts an exemplary synthesis of isosorbide esters according to an embodiment of the present method.
  • FIG. 2 shows a chromatogram of results obtained from quantitative analysis conducted by gas chromatography (GC) of isomers synthesized according to an embodiment of the present invention.
  • FIG. 3 is a graph showing the relationship between the percent catalyst load of phosphonic acid (H 3 PO 3 ) and its impact on APHA values and percent conversion of isosorbide when reacted at 175° C., 7 hours.
  • FIG. 4 shows a series of photos of the respective degree of color attenuation in isohexide ester product mixtures that have been reacted with H 3 PO 3 catalyst (175° C., 7 h.), as compared to stock solution of 2-ethyl-hexanoic acid (2EH).
  • FIG. 5 shows photos of APHA color attenuation in isohexide product mixtures prepared from a pre-distilled solution of 2EH (APHA 6) using phosphonic acid catalyst loads of 1 wt. % and 5 wt. %, respectively at 205° C., 7 hours.
  • FIG. 6 are photos of the results of a high temperature thermal stress tests for about 10 g. of isosorbide product mixture, which was subjected to 200° C. for 1 hour in air.
  • 1,4:3,6-dianhydrohexitols are a class of bicyclic furanodiols that are valued as renewable molecular entities.
  • 1,4:3,6-dianhydrohexitols will be referred to as “isohexides” in the Description hereinafter.
  • the isohexides are good chemical platforms that have recently received interest because of their intrinsic chiral bi-functionalities, which can permit a significant expansion of both existing and new derivative compounds that can be synthesized.
  • Isohexide starting materials can be obtained by known methods of making respectively isosorbide, isomannide, or isoidide.
  • Isosorbide and isomannide can be derived from the dehydration of the corresponding sugar alcohols, D-sorbitol and D mannitol.
  • isosorbide is also available easily from a manufacturer.
  • the third isomer, isoidide can be produced from L-idose, which rarely exists in nature and cannot be extracted from vegetal biomass. For this reason, researchers have been actively exploring different synthesis methodologies for isoidide.
  • the isoidide starting material can be prepared by epimerization from isosorbide. In L. W. Wright, J. D. Brandner, J. Org.
  • L-iditol precursor for isoidide
  • L-sorbose U.S. Patent Publication No. 2006/0096588; U.S. Pat. No. 7,674,381 B2
  • L-iditol is prepared starting from sorbitol.
  • sorbitol is converted by fermentation into L-sorbose, which is subsequently hydrogenated into a mixture of D-sorbitol and L-iditol.
  • This mixture is then converted into a mixture of L-iditol and L-sorbose. After separation from the L-sorbose, the L-iditol can be converted into isoidide. Thus, sorbitol is converted into isoidide in a four-step reaction, in a yield of about 50%.
  • Fischer-Speier esterification is the current standard protocol for industrial preparation of esters. Fischer-Speier esterification embodies a straightforward process for direct alcohol acylation with carboxylic acids employing Br ⁇ nsted or Lewis acid catalysts. However, color is problematic when converting thermally sensitive substrates such as isohexides in the presence of strong acid catalysts. The desire is to minimize downstream processing unit operations by developing a catalyst that can furnish relatively high yields (e.g., ⁇ 55%-60%) of target esters while minimizing color body formation or accretion.
  • esterification method In contrast to conventional commercial esterification protocols, which typically involve at least two operational steps a synthesis reaction followed with purification or decolorization (e.g., crystallization, distillation and/or chromatography) of the product the esterification method according to the present invention is simpler.
  • the method involves a single-step operation.
  • a process that can make either product which is or approaches colorlessness (so-called “water-white”), or product that is within tolerable color specifications, in a single reaction without further need for later purification would be quite advantageous in terms of cost and efficiency.
  • APHA APHA color standard
  • ASTM D1209 ASTM D1209
  • APHA is similar to the Hazen color scale test, which uses a platinum-cobalt (Pt/Co) solution, where the color of water could be used as a measure of concentration of dissolved and particulate material. Impurities can be deeply colored, for instance dissolved organic compounds such as tannins can result in dark brown colors.
  • the APHA color scale is from 0 to 500, where 0 is colorless and 500 is the most colored.
  • a feature of the present invention is the ability to reduce or eliminate color bodies that may be made in situ during esterification of an isohexide compound.
  • the color bodies are either prevented from forming or their amounts are minimized in the resultant product mixture.
  • the method involves: reacting an isohexide and a carboxylic acid, in the presence of a reducing Br ⁇ nsted acid catalyst for a time sufficient to yield a product mixture that exhibits an APHA value of less than 230.
  • the product mixture exhibits an APHA value of ⁇ 185, desirably the APHA value is ⁇ 150.
  • the isohexide can be at least one of: isosorbide, isomannide, and isoiodide.
  • the organic acid can be at least an alkanoic acid, alkenoic acid, alkynoic and aromatic acid, having C 2 -C 26 .
  • the isohexide is transformed to a corresponding ester at a conversion rate of at least 40%, desirably the conversion rate is about 50% or greater.
  • the esterification is performed at a temperature in a range from about 150° C. or 160° C. to about 240° C. or 250° C.
  • the reaction temperature is in a range from about 170° C. or 175° C. to about 205° C. or 220° C.
  • the reducing Br ⁇ nsted acid catalyst is present in an amount of at least 0.5 wt. % relative to the amount of isohexide. In certain embodiments, when the amount of reducing Br ⁇ nsted acid catalyst is >5.0 wt. %, the product mixture contains predominantly diesters. In other embodiments, when the reducing Br ⁇ nsted acid catalyst is present in an amount from about 2.5 wt. % to about 5.0 wt. %, the product mixture contains about a 1:1 ratio of monoesters and diesters. In still other embodiments, when the amount of reducing Br ⁇ nsted acid catalyst is present in an amount ⁇ 2.5 wt. %, the product mixture contains predominantly monoesters.
  • Table 1 lists several conventional acid catalyst species that have commercial or potential value as comparative examples in terms of product color, catalyst load, and conversion rate relative to a reducing Br ⁇ nsted acid.
  • the methods described herein are exemplified by use of phosphonic acid (H 3 PO 3 ) also known as phosphorus acid as the reducing Br ⁇ nsted acid.
  • H 3 PO 3 phosphonic acid
  • Table 1 the comparative examples tended to generate dark colored products with APHA values over 250.
  • a particular reducing Br ⁇ nsted acid species is phosphonic acid (H 3 PO 3 ), also known as phosphorus acid, which is a crystalline solid, commercially available, inexpensive, and possesses a strong acidity (pKa ⁇ 1).
  • This material evinces both high catalytic activity in the context of Fischer esterifications and pronounced color attenuation of the product mixture.
  • phosphonic acid has not received significant attention in this regard, either as a Br ⁇ nsted acid in the catalysis of isohexide acylation with carboxylic acids, concerning color mitigation of products or concerning high isohexide conversions. Further, at this time, phosphonic acid is one that manifests both high reactivity and concomitant color diminution.
  • phosphonic acid not only helps to catalyze and increase the conversion rate to make esters from isohexides, but also can help reduce significantly the development of undesired color bodies in the product mixture when used in sufficient quantities (e.g., ⁇ 1.0 wt. %; preferably ⁇ 1.5 wt. % or 2.0 wt. %).
  • Phosphonic acid manifests highly effective catalytic activity ( ⁇ 80%-95%) (i.e., efficacy similar to that exhibited for tin chlorides, ⁇ 87%-89%), in the esterification of isosorbide to mono and diesters of 2-ethylhexanoic acid, according to a particular embodiment.
  • Phosphonic acid proved to yield high isosorbide conversion to the corresponding mono- and diesters, while also displaying pronounced antioxidant properties that effectively controls and inhibits color body formation or accumulation in the product mixture.
  • Phosphonic acid functions as a catalyst for the acylation reaction, as well as provides a powerful reducing agent in solution that helps mitigate the formation of color bodies. Although not to be bound by theory, it is believed that the phosphonic acid may interact with color-body precursors to prevent their transition to colored entities.
  • Scheme 1 illustrates one embodiment of the reaction. The reaction is performed neat.
  • the conversion rate of isohexide to its corresponding esters is about least 40%-50%.
  • the isohexide conversion rate is about 55% or greater, more typically about 65% or 70% or greater (e.g., about 75%, 80%, 84%, 87%, 90%, 92%, 95%, or greater).
  • the method described herein are exemplified with 2-ethylhexanoic acid, the method is suitable for use with any organic acid desired for esterification with the isohexide, including alkanoic acid, alkenoic, and aromatic acids of C 2 to C 26 in size, provided only that the organic acid is soluble in the reaction mixture.
  • Phosphonic acid is reported to decompose to phosphoric acid and phosphine at 200° C., and yet doesn't seem to adversely affect the esterification process/color body mitigation at this temperature, as demonstrated by results in Table 2, where isosorbide manifested complete conversion to the corresponding esters, primarily diesters, with minimal color accretion from reactions carried out at 205° C. for 7 h.
  • Phosphonic Acid 5.48 98 100 @ 5 h As part of the process to minimize color, one can either pre-purify the staring reagents, for example, by distilling the alkanoic acid (also may use alkenoic or alkynoic acids) before esterification or perform follow-on chromatography, among other purification techniques.
  • phosphonic acid A unique feature of phosphonic acid is that it not only catalyzes the reaction, but has propitious reducing agent potential, and thus can further oxidize to phosphoric acid.
  • phosphonic acid In the area of isohexide esterification, phosphonic acid is the only catalyst of those screened to date, that discerns both high isosorbide conversion and color mitigation. Furthermore, no literature precedent for such behavior (aggressive catalysis, color mediation) was distinguished.
  • hypophosphorus acid H 3 PO 2
  • hypophosphorus acid H 3 PO 2
  • the kinetics of the reaction may be similar to that of the hypophosphorus and phosphonic acid as each has pKa near 1. Comparative catalyses for these acids, however, suggest that the chemistry that each of the acids display in mitigating color are likely dissimilar.
  • Hypophosphorus acid degrades at 130° C., and can be obtained only as a 50% aqueous solution, which because of the presence of water would not function in a similar manner as phosphonic acid in the present reaction system.
  • the present synthesis protocol for acid-catalyzed esterification of isohexides (e.g., isosorbide) with an carboxylic acid involves: A three-neck, 500 mL round bottomed flask equipped with a tapered, PTFE coated magnetic stir bar is charged with 50 g of isosorbide (0.342 mol), 148 g of 2-ethylhexanoic acid (1.026 mol) and 5 wt. % acid catalyst (relative to isosorbide).
  • FIG. 1 illustrates an embodiment of the present method for synthesizing isosorbide 2EH monoesters.
  • FIG. 2 is a representative chromatogram of the results obtained from quantitative analysis conducted by gas chromatography (GC) of the two sets of four isomers synthesized according to the reaction above.
  • GC gas chromatography
  • FIG. 3 is a graph showing the relationship between the percent catalyst load of phosphonic acid (H 3 PO 3 ) and its impact on APHA values and percent conversion of isosorbide when reacted at 175° C., 7 hours.
  • H 3 PO 3 percent catalyst load of phosphonic acid
  • FIG. 4 shows several photos of isosorbide product that have undergone acylation according to the present process.
  • the accompanying photos highlight the dual role catalytic and oxygen scavenging effect of phosphonic acid.
  • product mixture samples reacted (at 175° C. for 7 h) with phosphonic acid at 1 wt. % B, 2.5 wt. % C, 5 wt. % D, and 10 wt.
  • FIG. 5 are photos that show the decrease in APHA color value in isohexide product mixtures associated with an increase in phosphonic acid catalyst load of 1 wt. % and 5 wt. %, respectively (APHA 136, 98), as compared to a pre-distilled solution of 2EH (APHA 6) at 205° C., 7 hours.
  • FIG. 6 shows photos of the results of high temperature thermal stress tests to explore the oxygen scavenging potential of the acid catalyst for mitigating color.
  • the test sample contains about 10 g. of isosorbide product mixture, which was subjected to 200° C. for 1 hour in air.
  • the results suggest a window of good oxygen-scavenging performance and/or ability to incapacitate colored body precursors generated from thermal oxidiative decomposition of isosorbide in terms of the amount of phosphonic acid added to the isosorbide mixture.
  • An isosorbide product sample that contains no phosphonic acid exhibits very light clear color (APHA ⁇ 76), while at phosphonic acid amounts of about 90,000 ppm (900 mg) the solution exhibits a deep dark color (APHA 500).
  • the window has a lower and upper limit for the amount of phosphonic acid between about 2,000 ppm (0.2 wt. %) (APHA 98) to about 5,000 ppm (0.5 wt. %) or about 10,000 ppm (1.0 wt. %) that is effective at maintaining control of color body development to a relatively low level, at an APHA value between about 76 and about 105.
  • isosorbide shows the best performance when reacted using phosphonic acid catalyst, with better color attenuation relative to either isoiodide (APHA187) or isomannide (APHA 210). This may be a result of the nature of isomannide and isoidide. Isomannide is much more thermo-oxidatively unstable than isososorbide. Nonetheless, an APHA value of 210 for isomannide is far lower color production than typical. Normally, when isomannide is esterified with conventional catalyst the product would manifest an APHA color value of well over 500. In another example, isomannide reacts with 7.6 wt.
  • the particular isoiodide sample shown in the Table is about 80% pure, containing a significant amount of THF, which is a species that is readily susceptible to thermo-oxidative decomposition, and hence generation of color bodies. We believe that for an isoiodide sample of greater purity (e.g., near 100% purity) one will see a greater reduction in color than that indicated. The isoiodide product would have coloration comparable to or better than that of the isosorbide sample.
  • Polyesters can be made from the isohexide esters (e.g., isosorbide esters) having an APHA value of ⁇ 150 prepared according to the present method.
  • isohexide esters e.g., isosorbide esters

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  • Engineering & Computer Science (AREA)
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)
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US20140088226A1 (en) * 2011-06-21 2014-03-27 Evonik Degussa Gmbh Dianhydrohexitol diesters of 2-ethylheptanoic acid

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JP5379016B2 (ja) * 2007-10-31 2013-12-25 帝人株式会社 保存安定性が良好な無水糖アルコール組成物およびそれを用いるポリカーボネートの製造方法
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BR112016014052B1 (pt) 2021-07-27
EP3083635B1 (en) 2019-10-02
EP3083635A1 (en) 2016-10-26
WO2015094548A1 (en) 2015-06-25
HK1235051A1 (zh) 2018-03-02
MX2016007864A (es) 2016-09-07
CA2932265C (en) 2020-12-01
CN105814063B (zh) 2018-09-18
CA2932265A1 (en) 2015-06-25
BR112016014052A2 (pt) 2017-08-08
EP3083635A4 (en) 2017-04-26
KR20160098453A (ko) 2016-08-18
MX378510B (es) 2025-03-11
CN105814063A (zh) 2016-07-27
AU2014367102B2 (en) 2018-09-20

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